The present invention relates to a silver halide photographic light-sensitive material and an image-forming method using the light-sensitive material. Particularly, the present invention relates to a silver halide light-sensitive material to form an ultra-high contrast photographic image that is used in the fields of graphic art, and to an image-forming method using the light-sensitive material.
In a photomechanical process in the fields of graphic art, a method is used in which a photographic Ad image having continuous tone is converted into a so-called dot image, which expresses the contrast of an image by the size of a dot area, and this dot image is combined with an image obtained by taking photographs of character and line originals, to produce a printing original plate. It has been demanded that silver halide light-sensitive materials used for such a purpose have ultra-high contrast (particularly, xcex3 is 10 or more) photographic properties enabling clear separation of image portions from non-image portions, to improve the reproduction of characters, line originls, and dot images.
In the fields of graphic art, image-forming systems obtaining ultra-high contrast (particularly, xcex3 is 10 or more) photographic properties are disired, to obtain good reproduction of continuous tone images by dot images.
As a method for obtaining high-contrast photographic properties, a lithographic developing system, making use of the so-called xe2x80x9cinfectious development effectxe2x80x9d, has long been used. However, this system is very unstable with respect to oxidation of a developer by air, since the density of sulfurous ions in the developer is low, requiring much replenisher to keep the liquid activity stable.
Examples of an image-forming system that eliminates the instability of the lithographic developing system in the formation of an image, that ensures processing using a developer having high storage stability, and that makes it possible to obtain ultra-high contrast photographic properties, include systems described in U.S. Pat. Nos. 4,166,742, U.S. Pat. No. 4,168,977, U.S. Pat. No. 4,221,857, U.S. Pat. No. 4,224,401, U.S. Pat. No. 4,243,739, U.S. Pat. No. 4,269,922, U.S. Pat. No. 4,272,606, U.S. Pat. No. 4,311,781, U.S. Pat. No. 4,332,878, U.S. Pat. No. 4,618,574, U.S. Pat. No. 4,634,661, U.S. Pat. No. 4,681,836 and U.S. Pat. No. 5,650,746. In these systems, a surface-latent-image-type silver halide photographic light-sensitive material, to which a hydrazine derivative is added, is processed by a developer using, as the developing agent, hydroquinone/Metol or hydroquinone/phenidone having a pH of 11.0 to 12.3 and containing a sulfurous acid preservative in an amount of 0.15 mol/liter or more, to form an ultra-high contrast negative image having a xcex3 value exceeding 10. According to this method, ultra-high contrast and highly sensitive photographic properties can be obtained, and because a sulfite with a high concentration can be added in a developer, the stability of the developer against oxidation by air is extremely improved compared with the stability of a conventional lithographic developer.
Meanwhile, in the fields of photomechanical processes, there are demands for photographic light-sensitive materials excellent in image reproduction of an original, stable processing solutions, facilitated replenishment, and the like, to deal with the variation and complexity of printed products.
Particularly, originals to be used for a line portion-containing photographic step are made by applying photocomposition characters, handwriting characters, illustrations, and dotted photographs. In the originals, therefore, images differing in density and line width are intermingled, and there is hence a strong demand for a process camera, a photographic light-sensitive material, and an image-forming method that enable these originals to be reproduced with good image reproduction. In a mechanical process for catalogues or large-scale posters, expansion (division extension) or contraction (division contraction) of a dot photograph is widely practiced. In a mechanical process in which dots are expanded and used, the line density is roughened, leading to photography with blurred points. In a mechanical process in which dots. are contracted, the number of lines per inch is larger than that of the original, leading to photography of fine points. Therefore, an image-forming method having a wider latitude is needed, to keep the reproduction of dot gradation. In order to improve, particularly, the reproduction of dot images in the expansion (division extension) or contraction (division contraction) of a photograph composed of dots, and the reproduction of characters of originals in which Mincho/Gothic characters are intermingled, an image-forming method is sought that has a wide latitude not only providing ultra-high contrast photographic properties but also enabling reproduction of fine line image of originals and exact reproduction of dot images ranging from large dots to small dots.
To improve original reproduction, JP-A-3-39952 (the term xe2x80x9cJP-A-xe2x80x9d as used herein means an unexamined published Japanese patent application), JP-A-3-174143, JP-A-4-19647, or the like disclose a method in which an ultra-high contrast silver halide light-sensitive material having a multilayer structure, which includes a layer containing a redox compound that releases a development inhibitor by oxidation, and a light-sensitive silver halide emulsion layer containing a hydrazine derivative, is processed in a developer having a pH of 11 or more. In this method, the original reproduction is remarkably improved.
The above method, in which a surface-latent-image-type silver halide photographic light-sensitive material, to which a hydrazine derivative is added, is processed in a developer having a pH of 11.0 to 12.3, makes it possible to improve the stability of a developer by using a high-density sulfurous acid preservative. However, in order to obtain an ultra-high contrast photographic image, it is necessary to use a developer having a relatively high pH value. In this case, the developer tends to be oxidized by air, and it is therefore necessary to replenish a large amount of a developer. In view of this, various ideas, in which an ultra-high contrast photographic image-forming system utilizing nuclei formation developing of a hydrazine compound is realized using a developer having a lower pH, have been attempted.
In order to obtain an ultra-high contrast image by using a stable developer having a pH of less than 11.0, a method using a highly active hydrazine-type nucleating agent, and a nucleation accelerator, is disclosed in U.S. Pat. No. 4,269,929 (JP-A-61-267759), U.S. Pat. No. 4,737,452 (JP-A-60-179734), U.S. Pat. No. 5,104,769, and U.S. Pat. No. 4,798,780; JP-A-1-179939 and JP-A-1-179940; U.S. Pat. No. 4,998,604 and U.S. Pat. No. 4,994,365, and JP-A-8-272023.
In the processing using such an image-forming system, improvements in sharp dot quality and process stability are observed. However, further improvement is needed in view of reproduction of an original and a wide exposure latitude. Also, the above method cannot be said to be satisfactory in the point of original reproduction in the case of using the aforementioned redox compound that releases a development inhibitor by oxidation. There is a strong need to develop light-sensitive materials having higher original reproduction. Also, in view of environmental problems, which have been greatly emphasized in recent years, there is a strong need to develop light-sensitive materials that have small variation in the photographic properties, and that also have small variation in original reproduction, with variation in the composition of a developer, to decrease developer waste.
Meanwhile, Japanese patent No. 2709760 discloses a hydrazine-type redox compound that includes two sulfonamido groups and four or more repeating units of an ethyleneoxy group, and JP-A-9-269553 discloses a hydrazine-type redox compound that includes two sulfonamido groups in its molecule. However, these compounds also afford no possibility for producing silver halide photographic light-sensitive materials that have good reproduction of an original and are reduced in variations in photographic properties and in original reproduction with a variation in the composition of a developer, when processed in a low-pH developer.
In addition, Japanese patent No. 2656924 discloses a hydrazine-type redox compound containing a carboxyl group, and Japanese patent No. 2676439 discloses a hydrazine-type redox compound containing a sulfo group. However, even these compounds do not succeed in satisfying the requirement of silver halide photographic light-sensitive materials that have good reproduction of an original and suppressed black-spots, and that also have high sensitivity and contrast.
JA-P-4-122926, JP-A-7-43867, and JP-A-7-261310 disclose methods in which a light-sensitive material having a multilayer structure, comprising a layer containing a redox compound that releases a development inhibitor by oxidation, and a light-sensitive silver halide emulsion layer containing a hydrazine derivative and a nucleation development accelerator, is processed in a developer having a pH of 11 or less, to form an image improved in original reproduction.
As outlined above,improvement in original reproduction is a permanent object for light-sensitive materials used in graphic art, and there is a strong need for development of a system showing better reproduction of an original.
A first object of the present invention is to provide a silver halide photographic light-sensitive material that has high sensitivity, high contrast (e.g., xcex3 is 10 or more), and high maximum density (high Dmax) as its photographic properties, and that also shows excellent original reproduction.
A second object of the present invention is, in addition to the above object, to provide a silver halide photographic light-sensitive material that is reduced in the variations of sensitivity, xcex3, and Dmax, and that shows also excellent original reproduction, even if it is processed in a developer in which the density of sulfurous acid, introduced as a preservative, is decreased and the pH is changed by deterioration over time, or even if it is processed in a developer in which the pH is changed and the density of bromine ions is increased due to processing of a large number of films.
A third object of the present invention is to provide a silver halide photographic light-sensitive material that provides a highly stable and high-contrast image.
A fourth object of the present invention is to provide a silver halide photographic light-sensitive material having good dot quality and excellent original reproduction.
A fifth object of the present invention is to provide an image-forming method ensuring high sensitivity, w high contrast, and high Dmax, as photographic properties, and also excellent original reproduction.
A sixth object of the present invention, in addition to the above objects, is to provide a method of forming an image having wide exposure latitude and high dot quality.
Other and further objects, features, and advantages of the invention will appear more fully from the following description.
These objects of the present invention were attained by the following measures.
(1) A silver halide photographic light-sensitive material comprising at least one compound selected from the group consisting of the compounds represented by the following formula (1), (2) or (3): 
wherein R1 represents a phenyl group having at least one electron-withdrawing group as a substituent, or aromatic heterocyclic or aliphatic group, provided that when R1 is an alkyl group, it does not contain 4 or more repeating units of an ethyleneoxy group, PUG represents a residue of a development inhibitor, Y1 and Z1 respectively represent a substituent which is substitutable on a benzene ring, and n1 and p1 denote integers from 0 to 4; 
wherein Ar represents an aryl group or an aromatic heterocyclic group, PUG represents a residue of a development inhibitor, TIME represents a timing group and t denotes 0 or 1, wherein the group represented by Ar is substituted directly or indirectly by at least one dissociating group; 
wherein A represents a connecting group, m denotes an integer from 2 to 6, PUG represents a residue of a development inhibitor, TIME represents a timing group and t denotes 0 or 1.
(2) The silver halide photographic light-sensitive material as described in (1), comprising at least one of the compounds represented by the formula (1).
(3) The silver halide photographic light-sensitive material as described in (2), wherein R1 in the formula (1) is a phenyl group having at least one electron-withdrawing group as a substituent.
(4) The silver halide photographic light-sensitive material as described in (2), wherein the compound represented by the formula (1) has, as a substituent, at least one ballasting group or an (alkyl, aryl or heterocyclic)thio group.
(5).The silver halide photographic light-sensitive material as described in (1), comprising at least one redox compound represented by the formula (2).
(6) The silver halide photographic light-sensitive material as described in (5), wherein the redox compound represented by the formula (2) is represented by the following formula (2-1): 
wherein TIME, t, and PUG respectively have the same meaning as those in the formula (2), X2 represents a dissociating group or a substituent containing at least one dissociating group, Y2 and Z2 respectively represent a substituent which is substitutable on a benzene ring, m2 denotes an integer from 1 to 5, n2 and p2 denotes integers from 0 to 4, provided that the sum of m2 and n2 does not exceed 5 and when X2 includes a sulfo group (xe2x80x94SO3H) or its salt, it does not contain a pyridinio group as a substituent at the same time.
(7) The silver halide photographic light-sensitive material as described in (6), wherein the dissociating group in the formula (2-1) is selected from the group consisting of a carboxy group (xe2x80x94COOH), a sulfo group (xe2x80x94SO3H), xe2x80x94SO2NH2, xe2x80x94SO2NHCOxe2x80x94, xe2x80x94SO2NHCONHxe2x80x94, xe2x80x94NHSO2NHCOxe2x80x94, xe2x80x94CONHCOxe2x80x94, xe2x80x94SO2NHSO2xe2x80x94, and salts of these.
(8) The silver halide photographic light-sensitive material as described in (5), wherein the redox compound represented by the formula (2) contains at least one ballasting group as a substituent.
(9) The silver halide photographic light-sensitive material as described in (6) or (7), wherein at least one group represented by X2 or Y2 in the formula (2-1) is a ballasting group or a substituent substituted with a ballasting group.
(10) The silver halide photographic light-sensitive material as described in (5), wherein the redox compound represented by the formula (2) contains at least one alkylthio group, arylthio group or heterocyclic thio group as a substituent.
(11) The silver halide photographic light-sensitive material as described in (6) or (7), wherein at least one group represented by X2 or Y2 in the formula (2-1) is a substituent substituted with an alkylthio group, an arylthio group or a heterocyclic thio group.
(12) The silver halide photographic light-sensitive material as described in (1), comprising at least one redox compound represented by the formula (3).
(13) The silver halide photographic light-sensitive material as described in (12)i wherein the redox compound represented by the formula (3) is represented by the following formula (3-1) or (3-2): 
wherein Ar1 represents an m-valent aromatic or aromatic heterocyclic group, Ar2 represents a divalent aromatic or aromatic heterocyclic group, L2 represents an m-valent connecting group, and PUG, TIME, t and m respectively have the same meaning as those in the formula (3).
(14) The silver halide photographic light-sensitive material as described in (13), wherein the redox compound represented by the formula (3-2) is represented by the following formula (3-3) or (3-4): 
wherein Ar3 represents an m-valent aromatic or aromatic heterocyclic group, Ar4 represents a divalent aromatic or aromatic heterocyclic group, L4 represents an m-valent connecting group, TIME, t, PUG, and m respectively have the same meaning as those in the formula (3), Z3 represents a substituent which is substitutable on a benzene ring, and p3 denotes an integer from 0 to 4.
(15) The silver halide photographic light-sensitive material as described in any one of (12) to (14), wherein the redox compound is made to be contained by solid dispersion or polymer dispersion.
(16) The silver halide photographic light-sensitive material as described in any one of (1) to (15), comprising at least one nucleating agent.
(17) The silver halide photographic light-sensitive material as described in (16), comprising at least one nucleation accelerator.
(18) The silver halide photographic light-sensitive material as described in (17), comprising at least one quaternary salt compound represented by the formula (a), (b), (c), (d), (e) or (f): 
in the formula (a), Q1 represents a nitrogen atom or a phosphorous atom, R100, R110 and R120 respectively represent an aliphatic group, an aromatic group or a heterocyclic group and may be combined to form a ring structure, and M represents an m10-valent organic group which is combined with Q1+ by a carbon atom contained in M wherein m10 denotes an integer from 1 to 4;
in the formula (b), (c) or (d), A1, A2, A3, A4 and A5 respectively represent an organic residue for forming an unsaturated hetero ring containing a quaternary nitrogen atom, L10 and L20 respectively represent a divalent connecting group and R111, R222 and R333 respectively represent a substituent;
the quaternary salt compound represented by the formula (a), (b), (c) or (d) has, in its molecule, 20 or more of total repeating units of an ethyleneoxy group or propyleneoxy group, and these repeating units may be substituted on over plural positions; 
in the formula (e), Q2 represents a nitrogen atom or a phosphorous atom, R200, R210 and R220 respectively represent the same groups as defined for R100, R110 and R120 in the formula (a) respectively;
in the formula (f), A6 represents the same groups as defined for A1 or A2 in the formula (b) provided that the nitrogen-containing unsaturated hetero ring which A6 forms may have a substituent but does not contain a primary hydroxyl group on the substituent;
in the formulae (e) and (f), L30 represents an alkylene group, Y represents xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94SO2xe2x80x94, L40 represents a divalent connecting group having at least one hydrophilic group;
in the formulae (a) to (f), Xnxe2x88x92 represents an n-valent counter anion where n denotes an integer from 1 to 3, provided that when an anionic group is contained besides in a molecule and forms an intermolecular salt with Q1+, Q2+ or N+, Xnxe2x88x92 can be omitted.
(19) The silver halide photographic light-sensitive material as described in (18), comprising at least one compound represented by the formula (1), and at least one quaternary salt compound represented by the formula (b) or (f).
(20) A processing method of a silver halide photographic light-sensitive material, comprising developing the silver halide photographic light-sensitive material as described in any one of (1) to (19) by using a developer having a pH of 9.0 to 11.0 after the light-sensitive material is subjected to image exposure.
The silver halide photographic light-sensitive material of the present invention comprises at least one compound selected from the group consisting of the compounds represented by the aforementioned formulae (1) to (3).
Firstly, the compounds represented by the formula (1) for use of the present invention will be explained in detail.
R1 in the formula (1) represents a phenyl group having at least one electron-withdrawing group as a substituent, or aromatic helerocyclic or aliphatic group. When R1 represents an aromatic heterocyclic group, the aromatic heterocyclic group is a monocyclic or dicyclic and substituted or unsubstituted aromatic heterocyclic group having at least one nitrogen atom, oxygen atom or sulfur atom. Specific examples of the aromatic heterocyclic group include a pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, pyrrole ring, furan ring, thiophene ring, thiazole ring, and indole ring. The aliphatic group represented by R1 is an alkyl group, alkenyl group or alkinyl group, which is substituted or unsubstituted and straight-chain, branched or cyclic, provided that when R1 represents an alkyl group, 4 or more repeating units of an ethyleneoxy group are not contained in it. When R1 represents a phenyl group having at least one electron-withdrawing group as a substituent, the electron-withdrawing group means a substituent of which the Hammett""s substituent constant op has a positive value in the case of substituents disposed at the ortho or para position or a substituent of which the value om has a positive value in the case of substituents disposed at the meta position. Here, specific examples of the substituent whose op has a positive value include a halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxyl group, cyano group, (alkyl or aryl)sulfonyl group, sulfo group or its salts, sulfamoyl group, nitro group, thioureido group, sulfonamide group, imide group and alkyl group substituted with plural halogen atoms (e.g., xe2x80x94CF3 group). Examples of the substituent of which the value om has a positive value include, besides the same groups as those given as examples of the substituent of which the value op has a positive value, an acylamino group, ureido group, (alkoxy or aryloxy)carbonylamino group, sulfamoylamino group, (alkyl, aryl or heterocyclic)thio group, alkoxy group and aryloxy group.
When R1 represents a phenyl group, it may have two or more electron-withdrawing groups as substituents, and it may have an optional substituent other than the electron-withdrawing group.
The group represented by R1 may have optional substituents. In the present invention, examples of the optional substituent include a halogen atom (a fluorine atom, chlorine atom, bromine atom or iodine atom), alkyl group (including an aralkyl group, cycloalkyl group, active methine group and the like), alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing a quaternary nitrogen atom (e.g., pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or its salts, sulfonylcarbamoyl. group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy)carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic)amino group, nitrogen-containing heterocyclic group substituted with N, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy)carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio group, oxamoylamino group, (alkyl or aryl)sulfonylureide group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl or heterocyclic)thio group, (alkyl or aryl)sulfonyl group, (alkyl or aryl)sulfinyl group, sulfo group or its salts, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or its salts and groups containing a phosphoric acid amide or phosphate structure. These substituents may be further substituted with these substituents.
Y1 and Z1 in the formula (1) represent substituents that are substitutable on a benzene ring. Examples of Y1 and Z1 include the same substituents as those which the Ad above R1 may have. Preferable examples of Y1 and Z1 include a halogen atom, alkyl group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, imide group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, (alkyl, aryl or heterocyclic)thio group, sulfamoyl group, carbamoyl group, cyano group, and nitro group.
n1 and p1 in the formula (1) each represents an integer from 0 to 4. When n1 and p1 respectively are 2 or more, plural Y1 and Z1 may respectively be the same or different.
Examples of the development inhibitor given by the group represented by PUG in formula (1) include known development inhibitors having a heteroatom and combined directly with xe2x80x94C(xe2x95x90O)xe2x80x94 via the heteroatom. Specific examples of the development inhibitor may include mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzothiazoles, mercaptobenzoxazoles, mercaptothiadiazoles, benzotriazoles, benzimidazoles, indazoles, adenines, guanines, tetrazoles, tetrazaindenes, triazaindenes and mercaptoaryls. The development inhibitor given by the group represented by PUG is preferably a compound that restrains nuclei formation-infectious development. Specific examples of the compound include compounds having at least one or more nitro group or nitroso group, nitrogen-containing heterocyclic compounds such as pyridine, pyrazine, quinoline, quinoxaline and phenazine, and compounds adsorptive onto silver halide particles having an anionic charge group. Particularly, the compounds having a nitro group are preferable. Residues of these development inhibitors represented by PUG may have an optional substituent. More detailed explanations and specific examples concerning PUG include those described in Japanese Patent No. 2632056, page 11, column 22, line 38 to page 14, column 27, line 15, Japanese Patent No. 2676439, page 4, column 8, line 41 to page 5, column 10, line 10 and JP-A-9-269553, page 25, column 48, line 47 to page 26, column 50, line 17.
Next, a preferable range of the compound represented by the formula (1) will be explained.
The group represented by R1 in the formula (1) is preferably a phenyl group having at least one electron-withdrawing group. More preferable examples of the electron-withdrawing group include a halogen atom (particularly, a chlorine atom), alkoxycarbonyl group, carbamoyl group, sulfonamide group, thioureide group, sulfonyl group, m-acylamino group or m-ureide group which has a total carbon number of 0 to 30. Preferably the phenyl group represented by R1 has one or two electron-withdrawing groups.
In the formula (1), n, is preferably 0 or 1, and P1 is preferably 0.
Particularly preferable examples of Y1 of the formula (1) include a chlorine atom, alkyl group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, alkoxy group, alkoxycarbonyl group, and carbamoyl group.
Redox compounds represented by the formula (1) for use in the present invention includes a compound into which a ballasting group, which is commonly used in immobile photographic additives such as a coupler, or a polymer is incorporated. Among these, the compound into which a ballasting group is incorporated is one of the preferable compounds for use of the present invention. The ballasting group in the present invention represents a straight-chain or branched alkyl (or alkylene), alkoxy(or alkylenoxy), alkylamino(or alkyleneamino) or alkylthio group, having 6 or more carbon atoms, or a group having these groups as a partial structure, and more preferably a straight-chain or branched alkyl (or alkylene), alkoxy(or alkyleneoxy), alkylamino(or alkyleneamino) or alkylthio group, having 7 or more but 24 or less carbon atoms, or a group having these groups as a partial structure.
Although the ballasting group may be a substituent of any group of R1, Y1, and Z1 in the formula (1), it is preferably a substituent of the group represented by R1. More preferably, R1 is phenyl group substituted indirectly with the ballasting group.
As examples of the above polymer, those described in JP-A-1-100530 are given.
The redox compounds represented by formula (1) may contain a cationic group (e.g. a group containing a quaternary ammonio group, a group containing a quarternarized phosphorus atom, or a nitrogen-containing heterocyclic group containing a quarternarized nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group (provided that when R1 is an alkyl group, R1 does not contain 4 or more repeating units of an ethyleneoxy group); an alkyl-, aryl-, or heterocyclic-thio group, or a dissociating group (a group, or a partial structure, having a proton(s) of such low acidity that the proton is dissociable by an alkaline developer, e.g. carboxyl group/xe2x80x94COOH, sulfo group/xe2x80x94SO3H, phosphonic acid group/xe2x80x94PO3H, phosphoric acid group/xe2x80x94OPO3H, hydroxy group/xe2x80x94OH, mercapto group/xe2x80x94SH, xe2x80x94SO2NH2, N-substituted sulfonamide group/xe2x80x94SO2NHxe2x80x94, xe2x80x94CONHSO2xe2x80x94, xe2x80x94CONHSO2NHxe2x80x94, xe2x80x94NHCONHSO2xe2x80x94, xe2x80x94SO2NHSO2, xe2x80x94CONHCOxe2x80x94, an activated methylene group, xe2x80x94NHxe2x80x94 present in a nitrogen-containing heterocyclic group, or salts of these groups). Examples of the compounds containing these groups include those described, for example, in JP-A-7-234471, JP-A-5-333466, JP-A-6-19032, JP-A-6-19031, JP-A-5-45761, U.S. Pat. Nos. 4,994,365 and 4,988,604, JP-A-7-259240, JP-A-7-5610, JP-A-7-244348, German Patent No. 4006032, and JP-A-11-7093.
The redox compound represented by the formula (1) containing an (alkyl, aryl or heterocyclic)thio group may be preferably used in the present invention. When an (alkyl, aryl or heterocyclic)thio group is contained in the redox compound represented by the formula (1), the thio group is preferably substituted on the group represented by R1 in the formula (1) directly or indirectly.
The redox compounds represented by formula (1) may contain an adsorptive group capable of being adsorbed onto the silver halide. Examples of the adsorptive group include an alkylthio group, an arylthio group, a thiourea group, a-thioamide group, a mercapto heterocyclic group, and a triazole group, described in U.S. Pat. Nos. 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045, JP-A-59-201046, JP-A-59-201047, JP-A-59-201048, JP-A-59-201049, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244, JP-A-63-234245, and JP-A-63-234246. Further, these adsorptive groups onto the silver halide may be modified into a precursor thereof. Examples of the precursor include those groups described in JP-A-2-285344.
The compound represented by the formula (2) used in the present invention will be explained in detail.
In the formula (2), Ar represents an aryl group or an aromatic heterocyclic group. The group represented by Ar is substituted with at least one dissociating group directly or indirectly.
When Ar in the formula (2) represents an aryl group, the aryl group is a monocyclic or dicyclic aryl group, specifically, a phenyl group and a naphthyl group. When Ar represents an aromatic heterocyclic group, the aromatic heterocyclic group is a monocyclic or dicyclic aromatic heterocyclic group including at least one nitrogen atom, oxygen atom or sulfur atom. Specific examples of the aromatic heterocyclic group include groups having a pyridine ring, quinoline ring, isoquinoline ring, pyrrole ring, furan ring, thiophene ring, thiazole ring and indole ring.
The aryl or aromatic heterocyclic group represented by Ar in the formula (2) may have an optional substituent.
Examples of the optional substituent include a halogen atom (a fluorine atom, chlorine atom, bromine atom or iodine atom), alkyl group (including an aralkyl group, cycloalkyl group, active methine group and the like), alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing a quaternary nitrogen atom (e.g., pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or its salts, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including a group containing a repeating unit of ethyleneoxy or propyleneoxy), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy)carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic)amino group, nitrogen-containing heterocyclic group substituted with N, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy)carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary-ammonio group, oxamoylamino group, (alkyl or aryl)sulfonylureide group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl or heterocyclic)thio group, (alkyl or aryl)sulfonyl group, (alkyl or aryl)sulfinyl group, sulfo group or its salts, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or its salts and groups containing a phosphoric acid amide or phosphate structure.
These substituents may be further substituted with these substituents.
The group represented by Ar in the formula (2) is substituted with at least one dissociating group directly or indirectly. Here, the dissociating group is a group or partial structure having a low acidic dissociating proton in an alkaline developer or its salts. Specific examples of the dissociating group include a carboxy group (xe2x80x94COOH), sulfo group (xe2x80x94SO3H), phosphonic acid group (xe2x80x94PO3H), phosphoric acid group (xe2x80x94OPO3Hxe2x80x94), xe2x80x94SO2NH2, xe2x80x94SO2NHCOxe2x80x94, xe2x80x94SO2NHCONHxe2x80x94, xe2x80x94NHSO2NHCOxe2x80x94, xe2x80x94SO2NHSO2xe2x80x94, xe2x80x94CONHCOxe2x80x94, and activated methylene group, or salts of these groups. However, a mercapto group (xe2x80x94SH), xe2x80x94NHxe2x80x94 present in a nitrogen-containing heterocyclic group, xe2x80x94OH, and N-substituted substituted sulfonamide group (xe2x80x94SO2NHxe2x80x94) are excluded from the dissociating group. Here, the activated methylene group means a methylene or methine group sandwiched between two or three electron-withdrawing groups. The electron-withdrawing group is an atomic group of which the Hammett""s substituent constant op can have a positive value. Specific examples of the electron-withdrawing group include a carbonyl group, sulfonyl group, phosphonyl group, or groups including these atomic groups (e.g., an oxycarbonyl group, carbamoyl group, sulfamoyl group, and formyl group), imino group, cyano group and nitro group. Two of these electron-withdrawing groups may be combined to form a ring structure.
When the dissociating group is indirectly combined with the Ar group, the aforementioned optional substituents which the Ar group may have or combinations of these substituents are given as examples of the connecting group between the dissociating group and the Ar group. When the dissociating group is divalent, the style of substitution may be any one of left and right side substitutions, and as a group to be substituted on the dissociating group on the side opposite to the connecting group connected to the Ar side, a substitutable group is selected from optional substituents which the Ar group may have. It is to be noted that, when the dissociating group represents a sulfo group or its salt, the group represented by Ar in the formula (2) never has a pyridinio group as a substituent. Also, when the dissociating group represents xe2x80x94COOH, it is necessary that t is 0, or the xe2x80x94COOH be connected to the Ar group via a sulfonamide group (xe2x80x94SO2NHxe2x80x94) when t is 1.
In the present invention, examples of the salts of the dissociating group include salts comprising alkali metal ions, alkali earth metal ions, organic ammonium ions and organic phosphonium ions, such as a sodium cation, potassium cation, lithium cation, magnesium cation and tetrabutylammonium cation.
When the aryl or aromatic heterocyclic group represented by Ar in the formula (2) has a separate substituent other than the aforementioned dissociating group or the substituent containing the dissociating group, preferable examples of the separate substituent include an alkyl group, acylamino group, sulfonamide group, ureide group, sulfamoylamino group, imide group, thioureide group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, (alkyl, aryl or heterocyclic)thio group, sulfamoyl group, halogen atom, cyano group, and nitro group.
As examples of the residue of a development inhibitor represented by PUG in the formula (2), known residues of a development inhibitor which have a heteroatom and are bound with xe2x80x94C(xe2x95x90O)xe2x80x94(TIME)txe2x80x94 through the heteroatom. Specific examples and preferable examples of these residues are the same as those explained for PUG in the formula (1).
The timing group represented by TIME in the formula (2) represents a divalent connecting group which can release the group represented by (TIME)txe2x80x94PUG by a hydrolysis reaction of a developer in succession after the Acompound represented by the formula (2) is oxidized during developing, and further can releases PUG from the group represented by (TIME)txe2x80x94PUG through reactions run in one or more stages.
Detailed explanations and specific examples concerning the timing group represented by TIME include in Japanese Patent No. 2632056, page 4, column 8, line 10 to page 11, column 22, line 35, Japanese Patent No. 2676439, page 4, column 7, line 39 to page 4, column 8, line 40 and JP-A-9-269553, page 47, column 47, line 45 to page 47, column 48, line 46.
Next, a preferable range of the redox compound represented by the formula (2) will be explained.
The group represented by Ar in the formula (2) is preferably an aryl group and more preferably a phenyl group.
Preferable examples of the dissociating group which Ar contains as a direct or indirect substituent include carboxy group, sulfo group, phosphonic acid group, xe2x80x94SO2NH2, xe2x80x94SO2NHCOxe2x80x94, xe2x80x94SO2NHCONHxe2x80x94, xe2x80x94NHSO2NHCOxe2x80x94, xe2x80x94SO2NHSO2xe2x80x94, xe2x80x94CONHCOxe2x80x94 and activated methylene group or salts of these groups. Particularly preferable examples are carboxy group, sulfo group, xe2x80x94SO2NH2, xe2x80x94SO2NHCOxe2x80x94, xe2x80x94SO2NHCONHxe2x80x94, xe2x80x94NHSO2NHCOxe2x80x94 or salts of these groups. As the salts of these groups, a sodium cation or potassium cation is more preferable.
When t is 0 in the formula (2), preferable examples of the residue of a development inhibitor represented by PUG are residues of benzimidazoles, indazoles, benzotriazoles and pyrazoles having a nitro group. Among these residues, residues of indazoles are particularly preferable. When t is 1, preferable examples of the residue of a development inhibitor represented by PUG are residues of benzimidazoles, indazoles, benzotriazoles, mercaptotetrazoles, mercaptobenzimidazoles, mercaptobenzothiazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptotriazoles or pyrazoles containing a nitro group. Among these residues, residues of indazoles, benzotriazoles, mercaptotetrazoles, mercaptobenzimidazoles, mercaptobenzothiazoles or mercaptobenzoxazoles are more preferable and residues of indazoles, benzotriazoles or mercaptotetrazoles are particularly preferred.
As the timing group represented by TIME in the formula (2), timing groups represented by the formulae (T-1), (T-2) and (T-3) described in Japanese Patent No. 2632056 are preferable and the timing groups represented by the formula (T-1) are particularly preferable.
In the formula (2), t is more preferably 0.
Among the compounds represented by the formula (2), more preferable compounds are represented by the following formula (2-1). 
TIME, t and PUG in the formula (2-1) are the same as those in the formula (2) and each preferable range of them is also the same as that in the formula (2).
X2 represents a dissociating group or a substituent having at least one dissociating group. Y2 and Z2 respectively represent a substituent that can be substituted on a benzene ring. m2 represents an integer from 1 to 5 and n2 and p2 represent integers from 0 to 4, provided that the sum of m2 and n2 never exceeds 5. When X2 has the dissociating group represents a sulfo group (xe2x80x94SO3H), or a salt thereof, the case where the group represented by X2 has a pyridinio group, as a substituent, is excluded. When m2, n2 or p2 is an integer of 2 or more, a plurality of X2, Y2 or Z2 may be the same or different.
Here, the substituents represented by Y2 and Z2 show groups except for dissociating groups among optional substituents which the Ar group in the formula (2) may have. Preferable examples of the substituent are an alkyl group, acylamino group, sulfonamide group, ureide group, sulfamoylamino group, imide group, thioureide group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, (alkyl, aryl or heterocyclic)thio group, sulfamoyl group, halogen atom, cyano group and nitro group.
In the formula (2-1), p2 is preferably 0, n2 is preferably 0 or 1 and m2 is preferably 1 or 2.
In the formula (2-1), X2 is preferably groups having the following dissociating group (or its salt). Specifically, preferable examples of X2 include groups having xe2x80x94COOH, xe2x80x94Oxe2x80x94Lxe2x80x94COOH, xe2x80x94Sxe2x80x94Lxe2x80x94COOH, xe2x80x94CONHxe2x80x94Lxe2x80x94COOH, xe2x80x94COOxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCOxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCONHxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCON(xe2x80x94Lxe2x80x94COOH)2, xe2x80x94NHCONR500xe2x80x94Lxe2x80x94COOH, xe2x80x94NHSO2xe2x80x94Lxe2x80x94COOH, xe2x80x94NHP(xe2x95x90O)(Oxe2x80x94Lxe2x80x94COOH)2, xe2x80x94SO2NHxe2x80x94Lxe2x80x94COOH, xe2x80x94Lxe2x80x94COOH, xe2x80x94SO3H, xe2x80x94Oxe2x80x94Lxe2x80x94SO3H, xe2x80x94Sxe2x80x94Lxe2x80x94SO3H, xe2x80x94CONHxe2x80x94 Lxe2x80x94SO3H, xe2x80x94CONHxe2x80x94Lxe2x80x94SO2NH2, xe2x80x94COOxe2x80x94Lxe2x80x94SO3H, xe2x80x94COOxe2x80x94Lxe2x80x94SO2NH2, xe2x80x94NHCOxe2x80x94 Lxe2x80x94SO3H, xe2x80x94NHCONHxe2x80x94Lxe2x80x94SO3H, xe2x80x94NHCONHxe2x80x94Lxe2x80x94SO2NH2, xe2x80x94NHCON(xe2x80x94Lxe2x80x94SO3H)2, xe2x80x94NHCONR500xe2x80x94Lxe2x80x94SO3H, xe2x80x94NHCONR500xe2x80x94Lxe2x80x94SO2NH2, xe2x80x94NHSO2xe2x80x94Lxe2x80x94SO3H, xe2x80x94NHP(xe2x95x90O)(Oxe2x80x94Lxe2x80x94SO3H)2, xe2x80x94SO2NHxe2x80x94Lxe2x80x94SO3H, xe2x80x94Lxe2x80x94SO3H, xe2x80x94CONHCOxe2x80x94R500, xe2x80x94CONHSO2xe2x80x94R500, xe2x80x94CONHSO2NHxe2x80x94R500, xe2x80x94NHCONHSO2xe2x80x94R500, xe2x80x94NHSO2NHSO2xe2x80x94R500, xe2x80x94SO2NHSO2xe2x80x94R500 or salts of these groups.
Here, L represents a divalent connecting group having at least one alkylene group (preferably 1 to 20 carbon atoms) or a phenylene group and may contain one of or a combination of xe2x80x94Oxe2x80x94, xe2x80x94NR510xe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94, xe2x80x94SOxe2x80x94 and xe2x80x94POxe2x80x94. Also, L may have an optional substituent. As examples of the substituent, optional substituents which the Ar group in the formula (2) may have are given. These substituents may be dissociating groups. R500 represents a monovalent aliphatic group (preferably 1-20 carbon atoms), aromatic group (preferably 6 to 20 carbon atoms) or heterocyclic group (preferably five- to seven-membered rings having at least one nitrogen atom, sulfur atom or oxygen atom). R510 represents a hydrogen atom, monovalent aliphatic group (preferably 1-20 carbon atoms), monovalent aromatic group (preferably 6 to 20 carbon atoms) or monovalent heterocyclic group (preferably five- to seven-membered rings having at least one nitrogen atom, sulfur atom or oxygen atom).
More preferable examples of X2 in the formula (2-1) include groups having xe2x80x94Oxe2x80x94Lxe2x80x94COOH, xe2x80x94CONHxe2x80x94Lxe2x80x94COOH, xe2x80x94COOxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCOxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCONHxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCONR500xe2x80x94Lxe2x80x94COOH, xe2x80x94CONHxe2x80x94Lxe2x80x94 SO3H, xe2x80x94COOxe2x80x94Lxe2x80x94SO3H, xe2x80x94NHCONHxe2x80x94Lxe2x80x94SO3H, xe2x80x94NHCONR500xe2x80x94Lxe2x80x94SO3H, xe2x80x94CONHCOxe2x80x94R500, xe2x80x94CONHSO2xe2x80x94R500, xe2x80x94CONHSO2NHxe2x80x94R500, xe2x80x94NHCONHSO2xe2x80x94R500, xe2x80x94NHSO2NHSO2xe2x80x94R500, xe2x80x94SO2NHSO2xe2x80x94R500 or salts of these groups. Particularly preferable examples of X2 are groups having xe2x80x94CONHxe2x80x94Lxe2x80x94COOH, xe2x80x94COOxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCOxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCONHxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCONR500xe2x80x94Lxe2x80x94COOH, xe2x80x94CONHxe2x80x94Lxe2x80x94SO3H, xe2x80x94NHCONHxe2x80x94Lxe2x80x94SO3H, xe2x80x94NHCONR500xe2x80x94Lxe2x80x94SO3H, xe2x80x94CONHSO2xe2x80x94R500, xe2x80x94CONHSO2NHxe2x80x94R500, xe2x80x94NHCONHSO2xe2x80x94R500, or salts of these groups. Most preferable examples of X2 are groups having xe2x80x94COOxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCOxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCONHxe2x80x94Lxe2x80x94COOH, xe2x80x94NHCONR500xe2x80x94Lxe2x80x94COOH, xe2x80x94CONHSO2xe2x80x94R500, xe2x80x94CONHSO2NHxe2x80x94R500, NHCONHSO2xe2x80x94R500, or salts of these groups.
Preferably, R500 represents a monovalent substituted or unsubstituted alkyl group, or a monovalent substituted or unsubstituted phenyl group.
Redox compounds represented by the formula (2) or (2-1) includes a compound into which a ballasting group, which is commonly used in immobile photographic additives such as a coupler, or a polymer is incorporated. Particularly, a redox compound represented by the formula (2) or (2-1) into which a ballasting group is incorporated is preferably used for this invention. The ballasting group has 6 or more carbon atoms and can be selected from a straight-chain or branched, alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), or alkylthio group, or a group having these groups as its partial structure. It is more preferable that the ballasting group is, having 7 or more but 24 or less carbon atoms, a straight-chain or branched, alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), or alkylthio group, or a group having these groups as its partial structure.
Although the ballasting group may be a substituent of any group of Ar, TIME and PUG in the formula (2), it is preferably a substituent of the group represented by Ar. More preferably, the ballasting group is substituted on the group represented by Ar indirectly. Further more preferable is the case where at least one of the groups represented by X2 or Y2 in the formula (2-1) is the ballasting group or a group substituted with the ballasting group.
Examples of the above polymer include those described, for example, in JP-A-1-100530.
The compound represented by the formula (2) or (2-1) may contain a cationic group (specifically, for example, a group containing a quaternary ammonio group, group containing a quaternary phosphorus atom, or a nitrogen-containing heterocyclic group containing a quaternary nitrogen atom), group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, or (alkyl, aryl or heterocyclic)thio group. When the dissociating group represents a sulfo group (xe2x80x94SO3H) or its salt, the group represented by Ar in the formula (2) does not contain a pyridinio group as a substituent. Examples of the compounds containing these groups include those described, for example, in JP-A-7-234471, JP-A-5-333466, JP-A-6-19032, JP-A-6-19031, JP-A-5-45761, U.S. Pat. Nos. 4,994,365 and 4,988,604, JP-A-7-259240, JP-A-7-5610, JP-A-7-244348, and German Patent No. 4006032.
The compound represented by the formula (2) or (2-1) and containing an (alkyl, aryl or heterocyclic)thio group is among those that may be preferably used in the present invention. When an (alkyl, aryl or heterocyclic)thio group is contained in the compound represented by the formula (2), the thio group is preferably substituted on the group represented by Ar in the formula (2) directly or indirectly. More preferably, the (alkyl, aryl or heterocyclic)thio group is substituted on the group represented by X2 or Y2 in the formula (2-1).
The redox compound represented by the formula (2) or (2-1) may contain an adsorptive group that adsorbs onto the silver halide. Examples of the adsorbing group include an alkylthio group, an arylthio group, a thiourea group, a thioamide group, a mercapto heterocyclic group, and a triazole group, described in U.S. Pat. Nos. 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045, JP-A-59-2201046, JP-A-59-201047, JP-A-59-201048, JP-A-59-201049, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244, JP-A-63-234245, and JP-A-63-234246. Further, these groups capable of being adsorbed onto the silver halide may be modified into a precursor thereof. Examples of the precursor include those groups described in JP-A-2-285344.
Next, the redox compound represented by the formula (3) and used in the present invention will be explained in detail.
The connecting group represented by A in the formula (3) shows polyvalent connecting groups comprising singly or in combinations of, groups such as an alkylene group (preferably 1 to 20 carbon atoms), arylene group (preferably 6 to 20 carbon atoms), heterocyclic group (preferably five- to seven-membered ring having at least one nitrogen atom, sulfur atom or oxygen atom, which may be a condensate), single bond, xe2x80x94Oxe2x80x94, xe2x80x94NR540xe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94, xe2x80x94SOxe2x80x94 and xe2x80x94POxe2x80x94. Here, R540 represents a hydrogen atom, monovalent aliphatic group (preferably 1 to 20 carbon atoms), monovalent aromatic group (preferably 6 to 20 carbon atoms) or monovalent heterocyclic group (preferably five- to seven-membered ring having at least one nitrogen atom, sulfur atom or oxygen atom). The connecting group represented by A may have an optional substituent as same as the substituents which R1 in the formula (2) may have.
As examples of the residue of a development inhibitor represented by PUG in the formula (3), known residues of a development inhibitor which have a heteroatom and are bound with xe2x80x94C(xe2x95x90O)xe2x80x94(TIME)txe2x80x94 through the heteroatom. Specific examples and preferable examples of these residues are the same as those explained for PUG in the formula (1).
The timing group represented by TIME in the formula (3) has the same meaning as the aforementioned TIME in the formula (2) and the details, specific examples and the like of the timing group are the same as those explained in the formula (2).
The connecting group represented by A in the formula (3) is preferably a connecting group having at least two arylene groups, and more preferably a connecting group at least two arylene groups and at least two sulfonamide groups (xe2x80x94SO2NHxe2x80x94). A connecting group having at least three arylene groups and at least two sulfonamide groups is most preferable.
Among the compounds represented by the formula (3), more preferable compounds are represented by the following formula (3-1) or (3-2). 
wherein Ar1 represents an aromatic or aromatic heterocyclic group having m valences, Ar2 represents a divalent aromatic or aromatic heterocyclic group, L2 represents a connecting group having m valences and PUG, TIME, t and m have the same meanings as those in the formula (3).
When Ar1 or Ar2 represents an aromatic group, the aromatic group is a monocyclic or dicyclic aromatic group having m valences or two valences. Specific examples of the aromatic group include a phenylene group and naphthylene group. When Ar1 or Ar2 represents an aromatic heterocyclic group, the aromatic heterocyclic group is a monocyclic or dicyclic aromatic heterocyclic group having m or two valences, including at least one nitrogen atom, oxygen atom or sulfur atom. Given as specific examples of the aromatic heterocyclic group are groups having a pyridine-ring, quinoline ring, isoquinoline ring, pyrrole ring, furan ring, thiophene ring, thiazole ring, and indole ring, or the like. The aromatic group or heterocyclic group represented by Ar1 or Ar2 may have an optional substituent.
The connecting group represented by L2 in the formula (3-2) shows connecting groups comprising singly, or in combinations, groups such as an alkylene group, arylene group, polyvalent heterocyclic group, single bond, xe2x80x94Oxe2x80x94, xe2x80x94NR530xe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94C(xe2x95x90S)xe2x80x94, xe2x80x94SOxe2x80x94 and xe2x80x94POxe2x80x94. Here, R530 represents a hydrogen atom, monovalent aliphatic group , monovalent aromatic group or monovalent heterocyclic group. The connecting group represented by L2 may have an optional substituent.
Next, a preferable range of the compound represented by the formula (3-1) or (3-2) will be explained.
The group represented by Ar1 or Ar2 in the formula (3-1) or (3-2) is preferably an aromatic group and more preferably a phenylene group.
When the group represented by Ar1 or Ar2 in the formula (3-1) or (3-2) has a substituent, preferable examples of the substituent are an alkyl group, acylamino group, sulfonamide group, ureide group, sulfamoylamino group, imide group, thioureide group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, (alkyl, aryl or heterocyclic)thio group, sulfamoyl group, halogen atom, cyano group and nitro group.
In the formula (3-1) or (3-2), preferable groups as PUG when t is 0 and preferable groups as PUG when t is 1 are the same as those given in the formula (2) respectively.
Preferable groups as the timing group represented by TIME in the formula (3-1) or (3-2) are also the same as those given in the formula (2).
In the formula (3-1) or (3-2), t is more preferably 0.
In the formula (3-1) or (3-2), m is more preferably 2 or 3 and particularly preferably 2.
A preferable one as the connecting group represented by L2 in the formula (3-2) is a polyvalent connecting group having a sulfonamide group. A more preferable one is a polyvalent connecting group having at least one of arylene, alkylene, and heterocyclic group, and at least two sulfonamide groups.
More preferable compounds among the compounds represented by the formula (3-1) or (3-2) are represented by the following formula (3-3) or (3-4). 
In the formulae (3-3) and (3-4), TIME, t, PUG and m have the same meanings as those in the formulae (3-1) and (3-2), and each preferable range is also the same. In the formulae (3-3) and (3-4), Ar3 and Ar4 respectively represent an aromatic or aromatic heterocyclic group. Ar3 is an m-valent group and Ar4 is a divalent group. Ar3 and Ar4 respectively have same meanings as Ar1 and Ar2 in the formulae (3-1) and (3-2). L4 in the formula (3-4) represents an m-valent connecting group. In the formulae (3-3) and (3-4), Z3 represents a substituent and p3 represents an integer from 0 to 4.
In the formulae (3-3) and (3-4), preferable examples of the substituent represented by Z3 are the same as the optional substituent which A in the formula (3) may have. Preferable examples of the substituent are an alkyl group, acylamino group, sulfonamide group, ureide group, sulfamoylamino group, imide group, thioureide group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, (alkyl, aryl or heterocyclic)thio group, sulfamoyl group, halogen atom, cyano group and nitro group.
In the formulae (3-3) and (3-4), p3 is preferably 1 or 0, and more preferably 0.
In the formula (3-3), as the aromatic group or aromatic heterocyclic group represented by Ar3, a phenylene group, naphthylene group or six- or five-membered aromatic heterocyclic group (specifically, groups having a pyridine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring or the like) is preferable. Ar3 in the formula (3-3) is particularly preferably a phenylene group or a naphthylene group.
As the aromatic group or aromatic heterocyclic group represented by Ar4 in the formula (3-4), a phenylene group is particularly preferable.
The m-valent connecting group represented by L4 in the formula (3-4) shows connecting groups comprising singly, or in combinations, groups such as an alkylene group, arylene group, polyvalent heterocyclic group, single bond, xe2x80x94Oxe2x80x94, xe2x80x94NR520xe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94SO2xe2x80x94 and xe2x80x94C(xe2x95x90S)xe2x80x94. Here, R520 represents a hydrogen atom, monovalent aliphatic group or monovalent aromatic group.
When L4 includes an arylene group, a phenylene group or a naphthylene group is preferable as the arylene group. Also, when L4 includes a polyvalent heterocyclic group, the heterocyclic group may be an aromatic or non-aromatic heterocyclic group, specifically, a nitrogen-containing heterocyclic group containing a quaternary nitrogen atom such as a pyridinio group. Specific examples of the heterocyclic group include 1,4-dioxane ring, piperazine ring, 2,4,8,10-tetraoxaspiro-(5,5)undecane ring, biphthalimide ring, 1,2,4,5-benzenetetracarboxydiimide ring, triazine ring and pyridine ring. Also, when L4 has an alkylene group, the alkylene group may be a cycloalkylene group. Examples of the cycloalkylene group include groups including a cyclopropane ring, cyclohexane ring, bicyclohexane ring, decaline ring, or norbornane ring.
The m-valent connecting group represented by L4 may have an optional substituent. Examples of the substituent includes the aforementioned substituents which A in the formula (3) may have, and the combinations thereof.
A particularly preferable m-valent connecting group represented by L4 in the formula (3-4) is a connecting group having at least one alkylene group, arylene group, polyvalent heterocyclic group or single bond.
The redox compound represented by the formula (3) may be those into which the same ballasting group or polymer as the ballasting group or polymer which may be commonly used in immobile photographic additives such as a coupler, as same as the ballasting group or the polymer incorporated in the compounds represented by the formula (2) or (2-1). The ballasting group in the formula (3) is preferably substituted on the group represented by A directly or indirectly. Further, in the formula (3-1) or (3-2), the ballasting group is preferably substituted on Ar1 or L2 directly or indirectly, and in the formula (3-3) or (3-4), the ballasting group is preferably substituted on Ar3 or L4 directly or indirectly.
The redox compound represented by the formula (3) may contain an adsorptive group that adsorbs onto the silver halide. Given as examples of such an adsorptive group are the groups given as the adsorptive group which the compound represented by the formula (2) or (2-1) may have.
The redox compound represented by the formula (3) may contain a cationic group (specifically, for example, a group containing a quaternary ammonio group, group containing a quaternary phosphorus atom or a nitrogen-containing heterocyclic group containing a quaternary nitrogen atom), group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group or (alkyl, aryl or heterocyclic)thio group. As examples containing these groups, the compounds given as the specific examples containing the above groups in relation to the compound represented by the formula (2) or (2-1) are given.